Adhesive crayon composition containing sorbitol-benzaldehyde reaction product as additive

ABSTRACT

An adhesive crayon consisting of (1) an adhesive resin soluble in a mixture of water and a water-miscible organic solvent, (2) water, (3) the organic solvent and (4) a reaction product of sorbitol and benzaldehyde with or without a boron compound has a constant hardness, excellent adhesiveness and good shapestability in a wide range of temperature and humidity.

United States Patent [1 1 Ando et a1. 7

[ Nov. 5, 1974 ADHESIVE CRAYON COMPOSITION CONTAININGSORBITOL-BENZALDEHYDE REACTION PRODUCT AS ADDITIVE [75] Inventors: TakuoAndo, lbaraki; Hiroyuki Yamazaki, Toyonaka, both of Japan [73] Assignee:Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha, Osaka-shi, Japan [22]Filed: Jan. 28, 1972 21 Appl. No.2 221,767

[30] Foreign Application Priority Data Feb. 3, 1971 Japan 46-4104 May31, 1971 Japan 46-38019 June 2, 1971 Japan 46-38896 [52] U.S. Cl.260/29.6 BM, 260/296 E [51] Int. Cl C09j 3/12, C08f 3/56, C09j 3/00,C09j 3/14 [58] Field of Search 260/296 E; 117/122 PA [56] ReferencesCited UNlTED STATES PATENTS 3,267,052 8/1966 Brennan 260/5 3,539,4816/1968 7 Parker 260/27 3,576,776 12/1968 Muszik 117/122 PrimaryExaminerWilliam H. Short Assistant Examiner-Peter F. Kulosky Attorney,Agent, or FirmClellc W. Upchurch [5 7 ABSTRACT 6 .Claims, No DrawingsADHESIVE CRAYON COMPOSITION CONTAINING SORBITOL-BENZALDEHYDE REACTIONPRODUCT AS ADDITIVE BACKGROUND OF THE INVENTION The present inventionrelates to a novel adhesive crayon, and more particularly to an adhesivecrayon having improved properties.

Recently, there has been marketed so-called adhesive crayon", i.e., anadhesive of stick type, which is prepared by admixing a water-solubleresin such' as polyvinyl pyrrolidone, water and a salt'of aliphatic.carboxylic acid such as sodium stearate at a high temperature and thenplacing the resultant viscous hot mass into containers such as employedfor lipsticks, as described in the specification of US. Pat. No.3,576,776.

Such an adhesive crayon is useful especially for office work because ofeasiness to handle thanconventional liquid adhesives. However, the knownadhesive crayon shows some disadvantages. For instance, the hardness ofthe crayon readily depends on temperature andlhu+ midity. Therefore, inhot season it may be too soft to.

OBJECTS OF THE INVENTION An object of the present invention is toprovide a novel adhesive crayon having improved properties.

Another object of the invention is to provide an adhesive crayon whichis free from any trouble'as above- 7 mentioned.

These and other objects of the invention will become apparent from thedescription hereinafter.

DESCRIPTION OF THE INVENTION It has now been found that theabove-mentioned objects can be accomplished in the development of anadhesive crayon comprising (1) an adhesive resin soluble in a mixture ofwater and a water-miscible organic solvent, (2) water, (3) the organicsolvent and (4) the reaction product of sorbitol and benzaldehyde withor without a boron compound.

The adhesive crayon of the present invention can maintain a constanthardness or adhesiveness in a considerably wide temperature and humidityrange. The crayon can be readily spread by rubbing it on a surface to bebonded to form a thin and uniform tilm. Besides,-

paper to be-bonded which may occur when in case a conventional liquidadhesive is used. The adhesive can be applied after packed in suitablecontainers made of paper, plastics, metal, and the like. The use ofcontainpletely hydrolyzed polyvinyl acetate, especially partiallyhydrolyzed polyvinyl acetate, or acetals or urethanates thereof;copolymers of a major part of vinyl acetate and a minor part of acopolymerizable monomer, e.g.-, olefines such as ethylene, propylene,ethylenically unsaturated carboxylic acids such as crotonic acid,acrylic acid, methacrylic acid, maleic acid, or anhydrides, salts,amides and esters thereof; partially or completely hydrolyzed productsof the said copolymers, or acetals or urethanates thereof; polyacrylicit can show an excellent initial adhesion. It maybe transparent, andaccordingly can be also preferably used to bond transparent sheets suchas cellophane.

The crayon can be readily prepared by admixing the starting componentsas before-mentioned for a short time under heating. The product can bereadily casted into a container because of its low viscosity. Aftersolidified by cooling, it does not transform the shape even in case ofmaintaining at 90C. for 10 minutes.

The adhesive crayon of the present invention is also free from troubles,such as tendency to thread or crease acid, or alkali metal or ammoniumsalts thereof; polyacrylic acid amide, polyvinyl pyrrolidone,polyethylene oxide, polyethylene imine, vinyl methyl ether-maleicanhydridev copolymer, and the like. Particularly, the use of a partiallyhydrolyzed vinyl acetate-crotonic acid copolymer is desirable,especially the same having 0.5 to ZOpercent by mole in crotonicacidcontents and 5 to 80 percent by mole in adegree of hydrolysis of vinylacetate units. Larger crotonic acid contents than 20 percent by mole andsmaller degree of hydrolysis than 5 percent'by mole tend to make lesseasy the molding of the crayon, smaller crotonic acid contents than 0.5percent by mole tend to make less tacky the crayon, and larger degree ofhydrolysis than 80 percent by mole tends to cause coagulation in thepreparation of the crayon.

Examples of the'water-miscible organic solvent are alcohols such asmethanol, ethanol, and isopropanol, polyliydricalcohols such as ethyleneglycol, propylene glycol, diethylene glycol, glycerin, pentaerythritol,tetritol, pentitol and he'xitol, ketones such as acetone, methyl ethylketone and cyclohexanone, esters such as methyl acetate andethyl-acetate, ethers such as diethyl ether, tetrahydrofuran, ethyleneglycol monoethyl ether and dioxane, N-methyl-Z-pyrrolidone,dimethylformamide, dimethylsulfoxide, N-dimethylacetamide, pyridine,aceton'itr'ile, and the like. A water-inmiscible organic solvent can bealso employed by preparing a water-miscible mixture of the same andanother ,solvent. The reaction product of sorbitol and benzaldehyde asused in the present invention is prepared by adding benzaldehyde into anaqueous solution of sorbitol, further adding'dropwise an acidic catalystsuch as sulphuric or phosphoric acid with agitation and maintaining pHvalue at about 1 and the reactiontemperature at about 25C. by cooling,recovering the solid product by filtering the slurry-like reactionmixture,

and washing with water and drying the product. The

' chemical structure of thus obtained product is not sure,

but is deemed as monobenzylidenesorbitol, dibenzylidenesorbitol,tribe-nzylidenesorbitol or mixtures acids such as orthoboric acid,metaboric acid and tetra-1 boric acid, borates such as ammonium borate,potassium borate, sodium borate and borax and boric esters such asmethyl borate and ethyl borate.

The reaction product of three components can be prepared by adding theboron compound to an aqueous solution of sorbitol at a room temperatureor an elevated temperature with agitation, leaving the solution untilits pH value falls to about 3, subjecting the solution to reaction withbenzaldehyde in the manner as aforementioned. Alternatively, the boroncompound may be added into a solution of sorbitol after the reaction ofsorbitol and benzaldehyde is partially or completely carried out. Theamount employed of boron.

compound and benzaldehyde is 0.1 to 2 moles and 1' to 3 moles to 1 moleof sorbitol, respectively.

In the present invention, it is essential to use all the said fourcomponents. Absence of either water or organic solvent results infailure of the formation of hemogeneous mass or in the formation of masshaving insufficient shape-stability and poor adhesive strength.

The ratio of the said four components may vary according to a kind ofresin and materials to be bonded. But, in general, it is suitablyemployed to combine them in the range of 5 to 40 parts by weight ofwater, to 60 parts by weight of the organic solvent and 0.2 to 20 partsby weight of the reaction product of sorbitol to 10 parts by weight ofthe adhesive resin.

If desired, a nonionic surface active agent as polyoxyethylene alkylether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester ofmonoglyceride of fatty acid may further be used to increase transparencyof the product. The suitable amount employed of the nonionic surfaceactive agent is 1 to 5 parts by weight to 10 parts by weight of theadhesive resin.

The adhesive crayon can be usually prepared by admixing the said fourcomponents in a mixer provided with a stirrer such as screw or fan underheating to give a viscous hot mass and pouring the mass into containers,or extruding the said hot mass through a nozzle, and then cooling themass until it solidifies.

If necessary, colorant, perfume, filler or pigment may be added. Higherfatty acids or fatty acid esters of higher alcohol may be combined forthe purpose of regulating a hardness of the product.

The adhesive crayon of the present invention is more particularlydescribed and explained by means of the following illustrative Examples,in which all part and percent are by weight unless otherwise described.

EXAMPLE 1 .lowed to cool. The operations as above-mentioned weresmoothly carried out because of a low viscosity of the hot mass. Theobtained adhesive crayon was transparent and colorless solid and occuredno discoloration nor clouding even after storage for a long-period.

The adhesive was coated by rubbing it on the surface of craft paper. Itcan be spread smoothly to form a uniform and thin film on the surfacewithout any thread- The initial adhesion of the adhesive crayon wasexcellent.

I The crayon showed almost constant hardness and adhesion under thevarious conditions of temperature and humidity, for example, 20C. andpercent RH, 5C. and 30 percent RH, and 35C. and 100 percent RH.

The crayon kept the constant shape even after exposed to a hightemperature of 100C. for 10 minutes.

The transformation of the shape of the crayon in case of its applicationwas not observed, and the crayon could be applied even on a narrow spot.

The test results were shown in Table l.

COMPARATIVE EXAMPLE 1 Four parts of hydrolyzed vinyl acetate-crotonicacid copolymer the same as employed in Example 1, one part of sodiumstearate, 3 parts of glycerin, 5 parts of water and 3.5 parts ofmethanol were admixed at 90C. for 8 hours. Thus obtained viscous hotmass was poured into a cylindrical container but with some troublesbecause of high viscosity of the hot mass. After cooling, the obtainedadhesive crayon having a white and cloudy appearance was applied on thesurface of craft paper, but a film having uneven thickness was formed onthe surface. The adhesive turned to yellow after placed for severaldays.

Under the condition of 5C. and 30 percent RH, the crayon became too hardto be smoothly applied. On the other hand, under the condition of 35C.and 100 percent RH, the adhesive became too soft to form a thin film onthe surface. The crayon partially melted after exposed to an elevatedtemperature of C. for several minutes.

The test results were shown in Table 1.

EXAMPLE 2 The procedure of Example 1 was repeated except that one partof polyoxyethylene lauryl ether was further added to the ingredients ofExample 1. Thus prepared crayon was more transparent than that ofExample 1 and letters could be readily read through the said adhesivelayer having a thickness of 2 cm. Other properties of the crayon wereapproximately the same as obtained in Example 1.

The results were shown in Table 1.

EXAMPLE 3 Four parts of polyvinyl alcohol (a degree of polymerization:1,700, a degree of hydrolysis: 88 percent by mole), 1.5 parts .of thereaction product of sorbitol aand benzaldehyde, 3 parts of glycerin, 6parts of water and 3.5 parts of dimethylformamide were admixed at C. for30 minutes. The resultant hot mass was poured into a cylindricalcontainer and then allowed to cool up to a room temperature.

The test results were shown in Table 1.

EXAMPLE 4 r The procedure of Example 3 was repeated except thatpolyvinyl pyrrolidone having a molecular weight of about 360,000 wasemployed instead of polyvinyl alcohol,

. The, results were shown in Table 1.

COMPARATIVE EXAMPLE 2 V A mixture of 47 parts of water, 14 parts ofglycerin and 7 parts of sodium stearate was heated at 90 C. for 1 hourwith agitation. Into the obtained solution 32 parts of polyvinylpyrrolidone having a molecular weight of about 360,000 was added and theagitation was continued at 90C. for 6 hours. Thus obtained viscous hotmass was poured into a cylindrical container and allowed to cool.Various properties of the adhesive crayon thus obtained were near tothose in Comparative Example 1.

The test results were shown in Table l.

v EXAMPLE 5 Five parts of polyvinyl acetate, 0.2 part of the reactionproduct of sorbitol and benzaldehyde, 2 parts of diethylene glycol and 5parts of methanol were kneaded and heated at 65C. for 10 minutes withagitaweight, bonded to another sheet of the same craft paper by applyingan adhesive and fixing the both sheets and then pressing for a certainperiod by means of a rubber roll loaded up to 30 kg. .in total weight.

X: The adhesive layer was peeled.

A: A part of paper layer was peeled.

0: Almost all the paper layer was peeled.

4. Hardness was measured according to Japanese Industrial Standard (JIS)K 2530 by using a penetrometer as used for asphalt and was shown by adepth of penetration for 3 sec. of a needle loaded up to 46.3 g. intotal weight.

5. The shape-stability was shown by the number of cycle of putting anadhesive crayon out and in repeatedly, which was packed in a cylindricalcontainer of mm. in diameter, made of polyethylene and provided with ascrew used for putting out and in a content, by

operating the screw until it became impossible to set the crayon in thecontainer.

the breaking state of paper layer, which is occured by peeling rapidly asheet of craft paper of 25 mm. X 100 mm. in size, 0.13 mm. in thicknessand 68.5 g./m. in

tion. The resultant mixture was poured into a cylindri- I EXAMPLE 7 calcontainer and allowed to cool up to a room temperature. Thus obtainedadhesive crayon was colorless and A Sorbltol 'l atl e as prepared asfollows: To a 70 transparent. percent aqueous solution of sorbitol wasadded boric The test results were shown in Table l. acid in the ratio ofequi-molar amount to the sorbitol M L 6 employed and the aqueoussolution was agitated at a room temperature for one hour. To the saidsolution The procedure i Ex l 5 was repeated except was added twiceamounts of benzaldehyde in molar rathat vinyl acetate-ethyl acrylatecopolymer (ethyl acry- 1 P adlus-ted t0 1 Wlth P p acld and latecontents; 20 percent b l was l d i the reactlon was carried out at 25C.for 10 hours. The stead of polyvinyl acetate, obtained white paste waswashed with water, and dried The test results w r ly i l b l l, to givea desired sorbitol derivat ve.

Table l v Hard- Shape- Ex. Initial adhesion ness stabil- No. PeelingShearing z... I... 1... 1.... I... 1.... 2m 2"... 1.... 1.... (10 itystrength strength (kg/cm) (kg/cm) (sec) (sec) (sec) (sec) (sec) (sec)(sec) (sec) (sec) (sec) mm) (cycle) 1 0.44 5.63 x A o o 0 0 o o o o 132100 2 0.35 4.17 x X X A 0 0 o .0 o o 158 100 3 0.27 3.91 x x A o o o o oo 0 180 100 4 0.30 4.06 X x A o o 0 0 0 o o .145 100 5 0.42 5.50 A o 0 oo o o o o o 122 100 6 0.38 4.99 x A 0 o o o o o o o 129 100 c 1 0.152.69 x x x x x x X x A 0 91 8 N C m Ex. 2 0.17 2.95 x x x x X x x x A o86 10 No.

(NOT Ten parts of hydrolyzed vinyl acetate-crotonic acid 1. The peelingstrength was measured by an autocopolymer (crotonic acid contents: 3percent by mole, graph in the manner of peeling an aluminum foilof adegree of hydrolysis of vinyl acetate un1tsz55 percent 0.06 mm. inthickness, which-was bonded to another by mole), 12.5 parts of water, 17.5 parts of methanol, same foil of 25 mm. X 100 mm. by applying anadhesive 17.5 parts of N-methyl-2-pyrrohdone, 7.5 parts of ethon thesurface of either foil within an area of 25 mm. ylene glycol and 3 partsof the sa d sorbitol der1vat1ve X 25 mm. at 20C. and 65 percent RH andfixi g t were admixed at 95C. for 10 mlnutes. The obtained foils andthen pressing at a pressure of 50 kg,/25 m hot mass was poured into acyl1ndr1cal contamer and X 25 mm., under the conditions of tensile rat f200 allowed to cool up to a room temperature. As a result, i d li 1f18() the adhesive crayon had the same appearance and 2. The shearingstrength was measured on the same P p as descl'lbed mp 2 sample as usedin the test of peeling strength under the The test results were Show InTable conditions of a tensile rate of 10 mm./min. and a shear-COMPARATIVE EXAMPLE 4 mg angle of 0. Y N 3. The initial adhesion wasmeasured by observing The procedure in Comparative Example 1 wasrepeated except that 10 parts of partially hydrolyzed vinylacetate-crotonic acid copolymer, 2.5 parts of so- 1 diurn stearate, 7.5parts of ethylene glycol, 12.5 parts starting materials.

The test results were shown in Table 2.

EXAMPLE 8 yvinyl acetate employed-in Example 10, 2.5 parts of sodiummyristate, 8 parts of glycerin, 10 parts of water and 10 parts ofmethanol were admixed at 90C. for 8 hours. The obtained adhesive hadthesame appearance The procedure in Comparative Example I was repeatedexcept that 10 parts of partially hydrolyzed .pol-

V v and properties as described'in Comparative Example 1.

The procedure in Example 7 was repeated except v that 2.5 parts ofpolyoxyethylene lauryl ether was 7 The e l'eslllts were Shown Tableadded to the ingredients of Example 7. Thus obtained COMPARATIVE EXAMPLE5 adhesive crayon was more transparent than that in Exp I ample 7 andletters were readily read throughv the said i adhesive layer having athickness of 2 cm. The adhesive p 'gi f gg ii zfggzg f gg gfi g gg g gigs had the Same propel-hes as desFrbed m Example erin and 7 parts ofsodium stearate were heated at The test results were shown m Tablg 90C.for one hour and then 32 parts of polyvinyl pyr- EXAMPLE 9 l5 rolidonchaving a molecular weight of 360,000 was A added and further admixed at90C. for 6 hours.

sorbitol derivative was prepared as follows. To a 70 The test resultswere Shown in Tame 3 percent aqueous solution of sorbitol was addedboric v acid in the ratio of twice molar amounts to the sorbitol EXAMPLE11 employed and the mixture was allowed to stand at a The proceduremExample 10 was repeated except temperature for one hour with p Afterthat vinyl acetate-maleic anhydride copolymer (maleic addmg mole ofbepzaldehyde- 9 the/Sam mlxture anhydride contents: 3 percent by mole, adegree of hypH.waS l q l g gg g g i and.then 5 drolysis of vinyl acetateunits: 90 percent by mole) was p g i 3 at or Ours to gwe a employedinstead of polyvinyl acetate. The obtained lfi- Sor h d 1 d t t adhesivecrayon was transparent and colorless, and the en P 0 pama y y m ace aapplying property and the'stabilities for temperature cmtomc copolymer(crotomc aicld cfmtemsi and humidity were satisfied .for practical use.percent by mole, a degree of hydrolys s of vinyl acetate The teistresults were shown in Table units: percent by mole),'15 parts'of water,20 parts I of methanol,'l5 parts of dimethylformamide, 6 parts ofEXAMPLE l2 glycerin and 4 parts of the said sorbitol derivative were 3 Asorbitol derivative was'prepared as w To a 70 kneaded at 90 for hvlscous percent aqueous solution of sorbitol was added borax hot masswas poured a 'cylmdn cal m and in the ratio of 0.25 mole to one mole ofthe sorbitol emanowed to cool The obtained adheswe crayon h ployed andthe agitation was carried out at a room tem-- tremely excellent p thesame as descnbed perature for one hour to occur reaction. After addingExample one mole of benzaldehyde and a small amount of anhytest Table,Qx umehlerisiet the r ii i nt e mixture was TABLE 2 Compressive PeelingShearing Initial adhesion (sec.) Sh apebreaking strength strength 7Hardness stabiht strength (kg/cm!) (kg/cm?) in) 15 20 130 ts Fflo' sotum 120 140 mm-) (W (g-l2 Him-a5) 7 81:: ierse aaaeas a 5588 ea 0.334.99 x A O O O O O O O O 80 100 203 0.15 2.69 X x x X X X X A O 91 s 74EZ we M mm M, fur her Subjected to reaction at 20C. for 24 hours to 7W7W give a desired sorbitol derivative.

F f hfi i -fi i On theother hand, 10 parts of vinyl methylethercompressmg vfamcal dlrectlcnswlt S- Sampbe maleic anhydridecopolymer (vinyl methyl ether con- Ng j gg and 0 m t Hess y tents: 50percent by mole), 8 parts of water, 12 parts usmg a E tes f 1 ofmethanol, 9 parts of dimethylformamide, 8 parts of EXAMPLE 10 v glycerinand L5 parts of the said sorbitol derivative 7, where kneaded at 90C.for 10 minutes.

The procedure in Example I was re f except The resultant viscous hotmass was poured into'a cythat 10 Parts of pamillly hydrolyzed polyvmyacetate lindrical container and allowed to cool up to a room (a degreeof hydrolysis: 6O percentby mole), 10 parts temperature I of parts ofmethanol 8 parts of N'methy The adhesive crayon thus Obtained was ratherwhite pyrmhdfimgi 8 P of ethylene glycol 3 parts o and the properties'such as shape-stability, applying the sorbltol denvat'v? the t asdesFr'bed m Exam property, stabiliti'es for temperature and humidity,iniple 7 were employed as Stamng mammals" tial tackiness and initialadhesion was satisfied for prac- The test results were shown in Tabletical us 1 colt r p ig5r v e nxn 4g e i d V The test results were shownin Table 3.-

EXAMPLE 13 9 7 that vinyl acetate-ethylene copolymer (ethylene contents:20 percent by mole) was employed as a copolymer. The obtained adhesivecrayon had the same prop-' erties as described in Example l2.

What we claim is: l.ln an adhesivecrayon comprising 1. an adhesive resinselected, from the group consisting of partially or completelyhydrolyzed polyvinyl Th test lt w h w i T bl 3, 5 acetate, hydrolyzedvinyl acetate-crotonic acid co- TABLE 3 Compressive Peeling ShearingInitial adhesion (sect) Shape breaking strength strength liurtlnessstability strength (kgjcmfi) (kg/cm?) tm t!" t n I45 In ten t inn lun(10- mm.) (cycle) (re/2111111 5) 2- 8;: s as 8 8 8 8 8 8 8 Zlill is ll0,22 3. 22 X X X A O 8 O O Y O at no use 0.22 3.25 x x A O O O O 90 1580.10 1.98 X X X, X X X X A 8 J2 70 0.14 2.03 x x x' x x x X A 103 8 m;

EXAMPLE l4 polymer, hydrolyzed vinyl acetate-maleic anhy- A sorbitolderivative was prepared as follows: To a 70 22 2 2 2 353 gggg gfgg'igg ii Percent aqueous solution of sorbitol was added borax met y z 1 a e 6thell 1e co ol mgr in the ratio of 0.25 mole to one mole of the sorbitolemand p y py gdone Y P y ployed and the mixture was agitated at a roomtemper- 2 water and t ature f0r.one hour to occur'reactlon quanmanvely'3. awater-miscible organic solvent the improvement After i furfher 2mines 9 benzaidehyde pH w which comprises incorporating therein areaction ad usted to l with sulfuric acid and then the reaction productprepared y reacting 1 mole of sorbitol was carried out at 25C for 24hours h obta med and l to 3 moles of benzaldehyde with or without whitepaste was washed with water and dried to glve a 01 to 2 m 01 es of aboron compoun water Said deslred sorbtol denvatwe' water-miscibleorganic solvent and said reaction On the other hand, 10 parts ofhydrolyzed vmy aceproduct being employed in the ratio of 5 to 40, 10

tate-crotonic acid copolymer (crotonic acid contents: 3 percent by mole,a degree of hydrolysis of vinyl acetate units: 55 percent by mole), 17parts of water, 9 parts of methanol, 9 parts of N-dimethylacetamide, 3parts of ethylene glycol and 3 parts of the said sorbitol derivativewere admixed at 95C. for 10 minutes. The obtained viscous hot mass waspoured into a cylindrical container and allowed to cool.

The test results were shown in Table 4.

EXAMPLE [5 The procedure in Example 14 was repeated except that 2.5parts of polyoxyethylene lauryl ether was further added to theingredients of Example 14.

The testresults were shown in Table 4.

EXAMPLE 16 A sorbitol derivative was prepared as follows: To a 70percent aqueous solution of sorbitol was added borax to 60 and'0.2 to 20parts by weight, respectively, to 10 parts by weight of said adhesiveresin.

2. The adhesive crayon of claim 1, wherein said boron compound is-amember selected from the group consisting of boric acid and borax.

3. The adhesive crayon of claim 1, wherein said adhesive resin is ahydrolyzed vinyl acetate-crotonic acid copolymer.

4. The adhesive crayon of claim 3, wherein said hy- 40 drolyzed vinylacetate-crotonic acid'copolymer has 5 20 percent by mole of crotonicacid contents.

5. The adhesive crayon of claim 1, wherein said water-miscible organicsolvent is at least one member selected from the group consisting ofmethanol, ethanol, ethylene glycol, diethylene glycol, glycerin,dimethylformamide, dimethylacetamide, N-methyl-2- pyrrolidone andethylene glycol monoethyl ether.

6. A process for preparing an adhesive crayon which comprises admixingin the ratio of equi-molar amount to the sor itol eml. 10 parts byweight of an adhesive resin selected ployed and the reaction was carriedout at a room temf th group i ti f ti ll or l t l perature withagitation. After adding 2 moles of benzalh d l d l i l acetate, h d l di l y F P was l to 1 Wlth Rhosphonf acld and tate-crotonic acidcopolymer, hydrolyzed vinyl L mlxtur? l g :9 fa i 30 for 24acetate-maleic anhydride copolymer, vinyl methyl Ours to glve a sotenvanvef ether-maleic anhydride copolymer, vinyl acetate- The procedurein Example 9 was repeated except I ethylene copolymer, hydrolyzed vinylacetatethat the said sorbitol derivative was employed to give ethylenecopolymer and polyvinyl pyrrolidone, an adhesive crayon. 2 5 40 b r h ft 1 The test results were shown in Table 4. Q..w.BFl Y W 1 t 9 FE??? ITABLE 4 sh Coniapresliive m Peeling Sheanng Inmal adhesion (Sm) Hardnessstab iiiiy st f ngt ho 15 120 an L15 ea sm lion 120 HO 00- mm.) 37016)(E-/2 -rb) x x A O O O O O O O me x X A O O O O O 79 100 )5 52 X A O O OO O O 76 100 182 3,846,363 1 l 12 3. to 60 parts by weight of awater-miscible ormoles of boron compound to 1 mole of sorbitol for ganicsolvent, and a short time under heating to give a viscous hot 4. 0.2 toparts by weight of a reaction product premass and molding the mass intoa sticky shape.

pared by reacting 1 mole of sorbitol and l to 3 moles of benzaldehydewith or without 0.1 to 2 5

1. IN AN ADHESIVE CRAYON COMPRISING
 1. AN ADHESIVE RESIN SELECTED FROMTHE GROUP CONSISTING OF PARTIALLY OR COMPLETELY HYDROLYZED POLYVINYLACETATE, HYDROLYZED VINYL ACETATE-CROTONIC ACID COPOLYMER, HYDROLYZEDVINYL ACETATE-MALEIC ANHYDRIDE COPOLYMER, VINYL METHYL ETHER-MALEICANHYDRIDE COPOLYMER, VINYL ACETATEETHYLENE COPOLYMER, HYDROLYZED VINYLACETATE-ETHYLENE COPOLYMER AND POLYVINYL PYRROLIDONE,
 2. WATER, AND 2.The adhesive crayon of claim 1, wherein said boron compound is a memberselected from the group consisting of boric acid and borax.
 2. water,and
 2. 5 to 40 parts by weight of water,
 3. 10 to 60 parts by weight ofa water-miscible organic solvent, and
 3. a water-miscible organicsolvent, the improvement which comprises incorporating therein areaction product prepared by reacting 1 mole of sorbitol and 1 to 3moles of benzaldehyde with or without 0.1 to 2 moles of a boroncompound; water, said water-miscible organic solvent and said reactionproduct being employed in the ratio of 5 to 40, 10 to 60 and 0.2 to 20parts by weight, respectively, to 10 parts by weight of said adhesiveresin.
 3. The adhesive crayon of claim 1, wherein said adhesive resin isa hydrolyzed vinyl acetate-crotonic acid copolymer.
 3. A WATER-MISCIBLEORGANIC SOLVENT, THE IMPROVEMENT WHICH COMPRISES INCORPORATING THEREIN AREACTION PRODUCT PREPARED BY REACTING 1 MOLE OF SORBITOL AND 1 TO 3MOLES OF BENZALDEHYDE WITH OR WITHOUT 0.1 TO 2 MOLES OF A BORONCOMPOUND; WATER, SAID WATER-MISCIBLE ORGANIC SOLVENT AND SAID REACTIONPRODUCT BEING EMPOLYED IN THE RATIO OF 5 TO 40, 10 TO 60 AND 0.2 TO 20PARTS BY WEIGHT, RESPECTIVELY, TO 10 PARTS BY WEIGHT OF SAID ADHESIVERESIN.
 4. The adhesive crayon of claim 3, wherein said hydrolyzed vinylacetate-crotonic acid copolymer has 5 - 20 percent by mole of crotonicacid contents.
 4. 0.2 to 20 parts by weight of a reaction productprepared by reacting 1 mole of sorbitol and 1 to 3 moles of benzaldehydewith or without 0.1 to 2 moles of boron compound to 1 mole of sorbitolfor a short time under heating to give a viscous hot mass and moldingthe mass into a sticky shape.
 5. The adhesive crayon of claim 1, whereinsaid water-miscible organic solvent is at least one member selected fromthe group consisting of methanol, ethanol, ethylene glycol, diethyleneglycol, glycerin, dimethylformamide, dimethylacetamide,N-methyl-2-pyrrolidone and ethylene glycol monoethyl ether.
 6. A processfor preparing an adhesive crayon which comprises admixing